CA2393515A1 - Method for producing o-chloromethyl benzoic acid chlorides - Google Patents
Method for producing o-chloromethyl benzoic acid chlorides Download PDFInfo
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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Abstract
The invention relates to a method for producing o-chloromethyl benzoic acid chlorides of formula (I), in which R1 to R4 can be the same or different and represent hydrogen C1-C4 alkyl, halogen or trifluoromethyl, by reacting benz o- condensed lactones of formula (II), in which R1 to R4 have the above-mention ed meaning, with thionyl chloride. The inventive method is characterized in tha t the reaction is carried out in the presence of catalytic quantities of a Lew is acid and in the presence of catalytic quantities of a phosphine derivative.< /SDOAB>
Description
dl 11 METHOD FOR PRDDUCING O-CHLORDMETHYL SERZDIC ACID CHLORIDES
The present invention relates to a process for preparing o-chloromethylbenzoyl chlorides of the formula I, Ry in which R1 to R4 can be identical or different and are hydrogen, C1-C9-alkyl, halogen or trifluoromethyl, by reacting benzo-fused lactones of the formula II;
The present invention relates to a process for preparing o-chloromethylbenzoyl chlorides of the formula I, Ry in which R1 to R4 can be identical or different and are hydrogen, C1-C9-alkyl, halogen or trifluoromethyl, by reacting benzo-fused lactones of the formula II;
R
II
R
in which R1 to R9 are as defined above, with gaseous or liquid phosgene, its dimers or trimers.
o-Chloromethyl-substituted benzoyl chlorides are important intermediates for preparing, for example, pesticidally active compounds as described in the patents EP-A 460 575, EP-A 463 488, WO-A 95/18789, WO-A
95/21154 and WO-A 97/15552.
o-Chloromethyl-substituted benzoyl chlorides can be prepared, for example, by reacting benzo-fused lactones with thionyl chloride or phosgene.
EP-A 676 389 describes the preparation of o-chloromethylbenzoyl chlorides from benzo-fused lactones using thionyl chloride in the presence of a catalyst.
To achieve complete conversion, reaction temperatures of 160-170°C are required, at which thionyl chloride is already partially decomposed, resulting in the formation of troublesome byproducts.
In WO-A 99/16743, the reaction with thionyl chloride is carried out in the presence of a quaternary ammonium salt and a Lewis acid at 90-100°C. However, quaternary ammonium salts are problematic from an environmental point of view and have the following technical disadvantages: owing to sublimation, parts of the plants may become blocked. Furthermore, the salts are hygroscopic, which may lead to water being introduced and to a higher consumption of chlorinating agent.
Finally, the ammonium salts interfere with the distillative purification of the o-chloromethylbenzoyl chlorides.
Carrying out the reaction using thionyl chloride as chlorinating agent is disadvantageous since sulfur dioxide, which has to be worked-up or neutralized, is formed as coproduct in the synthesis. If the chlorinating agent used is phosgene, carbon dioxide, which does not have to be disposed of, is the only byproduct.
EP-A 583 589 describes a process for preparing o-chloromethylbenzoyl chlorides by phosgenation of benzo-fused lactones in the presence of a catalyst at 170-180°C. In contrast to thionyl chloride, phosgene is thermally stable under these conditions; however, the handling of phosgene and its hold up in the condenser at the high temperatures involved is made more difficult by increased safety precautions. Furthermore, under these conditions, the reaction product is under high thermal stress, which may result in its partial decomposition.
In WO 97/12854, triarylphosphine oxides are used as special catalyst type for the reaction, owing to which the use of hydrogen chloride can be dispensed with;
however, this does not result in an improvement in the required reaction conditions with respect to the objectionably high reaction temperatures and the resulting safety precautions required.
It is an object of the present invention to provide an economical process, capable of being carried out on an industrial scale, for preparing o-chloromethylbenzoyl chlorides which does not have the abovementioned disadvantages and still affords high yields.
We have found that this object is achieved by the process mentioned at the outset, which comprises carrying out the reaction with phosgene, its dimers or trimers in the presence of catalytic amounts of a Lewis acid and catalytic amounts of a phosgenation catalyst.
The starting. materials used are benzo-fused lactones (phthalides) of the formula II, R
R
R"
II
in which R1 to R° can be identical or different and are hydrogen (H), Ci-C~-alkyl, halogen (fluorine, chlorine, bromine or iodine) or trifluoromethyl. Preference is given to using unsubstituted phthalide.
The chlorinating agent used is preferably gaseous or liquid phosgene. Furthermore, it is also possible to use dimers (trichloromethyl chloroformate, "diphosgene") or trimers of phosgene (bistrichloromethyl carbonate, "triphosgene") or mixtures of these chlorinating agents.
Suitable phosgenation catalysts are, in particular, nitrogen compounds and phosphorus compounds. Examples which can be considered are N,N-disubstituted formamides, hexaalkylguanidinium salts, trialkylphosphines or triarylphosphines which may be substituted or unsubstituted in the aryl moiety, trialkylphosphine oxides or triarylphosphine oxides which may be substituted or unsubstituted in the aryl moiety, N-substituted imidazoles and substituted or unsubstitited pyridines. Particular preference is given to the pyridines of the formula IIIa, IIIa i N
where R is hydrogen or methyl, and to phosphine oxides of the formula IIIb, O
~~~b R' P R m r Rr r in which R' to R" ' can be identical or different and are C1-C1o-alkyl or unsubstituted or C1-Cq-alkyl-substituted phenyl and the index n is 0 or 1.
Particular preference is given to 3-methylpyridine picoline) and unsubstituted triphenylphosphine oxide.
The use of liquid trialkylphosphine oxides has, in particular, technical advantages (no need to handle solids, easier discharge of the distillation residue during pu.rification). The tri-C6-C$-alkylphosphine oxides available under the trade name Cyanex~ (for example. Cyanex~ 923 from Cyanamide) are, for example, suitable here. Liquid trialkylphosphine oxides combined with Lewes acids, such as tri(C1-Cq-alkyl) borates and boric acid, have been found to be particularly useful.
The phosgenation catalyst is generally added in amounts of from 0.1 to-20 mol%, based on the amount of benzo-fused lactone used, and is preferably added in amounts of from 1 to 10 molo.
Suitable Lewes acids are, in particular, boron compounds, such as, in particular, BF3, BC13 or complexes thereof with oxygen compounds, sulfur compounds or nitrogen compounds, tri(C1-C9-alkyl) borates and boric acid (H3B03) itself. Furthermore suitable are A1C13, alkylaluminum dichlorides and dialkylaluminum chlorides, and heterogeneous Lewis-acidic alumosilicates of the zeolite type. Particular preference is given to BF3, BC13 and complexes thereof with ether (in particular diethyl ether), water (dehydrate), alcohol (in particular methanol), sulfide (in particular dimethyl sulfide) and amine (in particular ethylamine). Particularly suitable are, for example, BF3 etherate and BF3 dehydrate.
The Lewes acid used is particularly preferably boric acid or tri(C1-C4-alkyl) borate. Such processes give excellent yields and have the advantage that the reaction mixtures are free from fluoride ions. Compared to the analogous reaction where the Lewis acid used is BF3, the entire apparatus can be simplified.
The Lewis acid is added in amounts of from 0.1 to 20 mol%, based on the amount of benza-fused lactone used, preferably in amounts of from 0.5 to 5 mol%.
In a further preferred embodiment of the process, the catalyst used is a complex, formed beforehand, of Lewis acid and the phosgenation catalyst. In general, this complex is employed in a concentration of from 0.1 to mol%, based on the amount of benzo-fused lactone used. The catalyst used is preferably a complex of BF3 and a methyl-substituted pyridine, and particular 15 preference is given to the BF3-(3-picoline complex.
If desired, hydrogen chloride can be introduced in parallel to the introduction of phosgene, to accelerate ring-opening. However, the introduction of hydrogen 20 chloride during. the synthesis is preferably dispensed with.
Furthermore, it may be advantageous to employ heterogeneous Lewis-acidic catalysts, such as, for example, zeolites of the faujasite type in which some or all of the exchangeable cations have been replaced by protons. A heterogeneously catalyzed reaction has the advantage that it can be carried out in a fixed bed. The heterogeneous catalyst is employed in amounts of from 0.01 to loo by weight and preferably in amounts of from 0.1 to 1o by weight, based on the amount of benzo-fused lactone used.
The reaction temperature is generally 110-200°C and preferably 130-160°C.
The process is preferably carried out in the absence of a solvent. However, it is possible to add a solvent -which is inert to phosgene. Inert solvents are, for example, aromatic hydrocarbons, such as toluene, o-, m-or p-xylene or mixtures thereof, chlorinated aromatic hydrocarbons, such as chlorobenzene~ or dichloro-benzenes, or cyclic carbonates, such as ethylene carbonate or propylene carbonate.
The process can be carried out either continuously or batchwise.
The examples below serve to illustrate the process in more detail.
General process description for all examples:
In a phosgenation apparatus consisting of a 1 1 double-jacketed reactor fitted with a battery of high-efficiency condensers, in each case 2 mol (268 g) of phthalide were initially charged and molten together with the catalyst system in question. After heating to 140°C, gaseous phosgene was introduced until no more phosgene was consumed (noticeable by a decrease in the internal temperature). The mixture was then stirred at 140°C for 1 hour, and excess phosgene was then stripped at 100°C using nitrogen. In selected examples, the product was isolated by fractional distillation at 1 mbar and 93-95°C.
Example 1 9. 3 g (0. 1 mol, 5 mol o) of ~3-picoline (3-methyl-pyridine) and 7.9 g (0.04 mol, 2 molo) of BF3-diethyl ether complex ("BF3-etherate") were added as catalyst.
Over. a period of 8 h, a total of 218 g (2.18 mol) of gaseous phosgene were introduced at 140-145°C. After the excess phosgene had been stripped, the reaction discharge (387 g) contained 95 GC area s of o-chloromethylbenzoyl chloride and 2.5 GC area o of unreacted phthalide. Distillation of the crude discharge gave 350 g of o-chloromethylbenzoyl chloride (93% of theory) of a purity of 970.
Example 2 392 g (3 mol) of phthalide together with 14 g (0.15 mol) of ~-picoline and 12 g (0.06 mol) of BF3 etherate were heated to 140°C. At 140-145°C, a total of 342 g (3.42 mol) of gaseous phosgene were introduced.
After an extra reaction time of 1 h, the excess phosgene was stripped using nitrogen. The reaction discharge (572 g) contained 97 GC area % of o-chloromethylbenzoyl chloride and 1 GC area % of phthalide.
Example 3 The catalyst added comprised 20 g of a BF3-~-picoline complex, which had been prepared beforehand. Over a period of 6 h, a total of 230 g (2.3 mol) of gaseous phosgene were introduced. After the excess phosgene had been stripped, the reaction discharge (391 g) contained 97.2 GC area % of o-chloromethylbenzoyl chloride and 0.7 GC area % of phthalide. Distillation of the crude discharge gave 334 g of o-chloromethylbenzoyl chloride (880 of theory) of a purity of 98.80.
Example 4 2 mol of phthalide (268 g) were initially charged with 27.8 g of triphenylphosphine oxide (TPPO) (0.1 mol) and 1 g of HY zeolite GE 1967. At 140-149°C, a total of 231 g of gaseous phosgene (2.31 mol) were introduced over a period of 8 h. After an extra stirring time of 1 h at 140°C, the excess phosgene was stripped using nitrogen. The discharge (403 g) contained 78 GC area o of o-chloromethylbenzoyl chloride and 6.8% of phthalide.
Example 5 2 mol of phthalide (268 g) were initially charged with 27.8 g of TPPO (0.1 mol) and 7.9 g (0.04 mol) of BF3 etherate. At 140-150°C, a total of 233 g of gaseous phosgene (2.33 mol) were introduced over a period of 8 h. After an extra stirring time of 1 h at 140°C, the excess phosgene was stripped using nitrogen. The discharge (415 g) contained 88.4 GC area % of o-chloro-methylbenzoyl chloride and O.lo of phthalide.
Fractional distillation of the crude discharge gave 363 g (960 of theory) of o-chloromethylbenzoyl chloride of a purity of 99.80.
Example 6 268 g (2 mol) of phthalide, 9.3 g (0.1 mol) of (3-picoline and 50 ml of a 0.1 molar solution of BC13 in xylene were initially charged. At 140-150°C, a total of 200 g (2 mol) of gaseous phosgene was introduced over a period of 8 h. The mixture was then stirred at 140°C
for another hour. Excess phosgene was stripped using nitrogen, giving a discharge of 398 g having a content of 77.2 GC area % of o-chloromethylbenzoyl chloride and 10.9% of unreacted phthalide.
Example 7 268 g (2 mol) of phthalide, 9.3 g (0.1 mol) of (i-picoline and 3.1 g (0.05 mol) of crystalline boric acid (Riedel de Haen) were initially charged. At 140-150°C, a total of 245 g (2.45 mol) of gaseous phosgene was introduced over a period of 7 h. The mixture was then stirred at 140°C for another hour. Excess phosgene was stripped using nitrogen, giving a discharge of 380 g having a content of 96 GC area % of o-chloro-methylbenzoyl chloride and 1.40 of unreacted phthalide.
Fractional distillation of the crude discharge gave 340 g of o-chloromethylbenzoyl chloride (90% of theory) of a purity of > 970.
Example 8 268 g (2 mol) of phthalide, 27.8 g (0.1 mol) of TPPO
and 3.1 g (0.05 mol) of crystalline boric acid (Riedel de Haen) were initially charged. At 140-150°G, a total of 247 g (2.47 mol) of gaseous phosgene was introduced over a period of 5 h 45 min. The mixture was then stirred at 140°C for another hour. Excess phosgene was stripped using nitrogen, giving a discharge of 411 g having a content of 88 GC area o of o-chloromethylbenzoyl chloride and 0.7a of unreacted phthalide. Fractional distillation of the crude discharge gave 358 g of o-chloromethylbenzoyl chloride (940 of theory) of a purity of 98.50.
Example 9 268 g (2 mol) of phthalide, 27.8 g (0.1 mol) of TPPO
and 5.2 g (0.05 mol) of trimethyl borate (Aldrich) were initially charged. At 140-150°C, a total of 256 g (2.56 mol) of gaseous phosgene was introduced over a period of 7 h. The mixture was then stirred at 140°C
for another hour. Excess phosgene was stripped using nitrogen, giving a discharge of 410 g having a content of 87.6 GC area ~ of o-chloromethylbenzoyl chloride and 1.1o of unreacted phthalide.
Example 10 2 mol of phthalide, 34.8 g (0.1 mol) of cyanex 923 (Cyanamid) and 3.1 g (0.05 mol) of boric acid were initially charged. At 141 to 150°C, a total 257 g (2.57 mol) of phosgene was introduced over a period of 4 h. The mixture was stirred at 140°C for another hour, and excess phosgene was stripped using nitrogen. The ' CA 02393515 2002-06-05 a crude discharge of 417 g was subjected to fractional distillation. This gave 352 g (93~ of theory) of o-chloromethylbenzoyl chloride of a purity of 98.7%.
Example 11 2 mol of phthalide, 34.8 g (0.1 mol) of Cyanex 923 (Cyanamid) and 5.2 g (0.05 mol) of trimethyl borate were initially charged. At 141 to 150°C, a total of 244 g (2.44 mol) of phosgene was introduced over a period of 6 h. The mixture was stirred at 140°C for another hour, and excess phosgene was stripped using nitrogen. The crude discharge of 411 g was subjected to fractional distillation. This gave 357 g (940 of theory) of o-chloromethylbenzoyl chloride of a purity of 97.70.
Comparative Example I compared to WO-A 99/16743 According to the general experimental procedure, 9.1 g of triethylbenzylammonium chloride (TEBA) (0.04 mol, 2 mol%) and 7.9 g of BF3 etherate (0.09 mol, 2 molo) were used as catalyst mixture. Over a period of 11 h, a total of 45 g (0.45 mol) of gaseous phosgene was introduced at a reaction temperature of initially 95 100 ° C ( 3 h ) and then at 14 0 ° C . After an extra reaction time of 1 h at 140°C and stripping of the phosgene, the crude discharge contained only 7.7 GC area % of o-chloromethylbenzoyl chloride and 910 of unreacted phthalide.
Comparative Example I shows that the phosgenation reaction cannot be carried out under the conditions preferred in WO 99/16743.
r Comparative Example II compared with EP-A 583 589 2 mol of phthalide were initially charged with 18.6 g of (3-picoline (0.2 mol, 10 molo). At 142-152°C 209 g (2.1 mol) of gaseous phosgene and 154 g of gaseous HC1 were introduced in parallel over a period of 10 h.
After an extra stirring time and stripping of excess phosgene, the reaction discharge (380 g) contained 86%
of o-chloromethylbenzoyl chloride and 6~ of unreacted phthalide.
Comparative Example II shows that without the addition of a Lewis acid, the reaction proceeds considerably more slowly and with a poorer yield, and that furthermore more phosgenation catalyst is required.
II
R
in which R1 to R9 are as defined above, with gaseous or liquid phosgene, its dimers or trimers.
o-Chloromethyl-substituted benzoyl chlorides are important intermediates for preparing, for example, pesticidally active compounds as described in the patents EP-A 460 575, EP-A 463 488, WO-A 95/18789, WO-A
95/21154 and WO-A 97/15552.
o-Chloromethyl-substituted benzoyl chlorides can be prepared, for example, by reacting benzo-fused lactones with thionyl chloride or phosgene.
EP-A 676 389 describes the preparation of o-chloromethylbenzoyl chlorides from benzo-fused lactones using thionyl chloride in the presence of a catalyst.
To achieve complete conversion, reaction temperatures of 160-170°C are required, at which thionyl chloride is already partially decomposed, resulting in the formation of troublesome byproducts.
In WO-A 99/16743, the reaction with thionyl chloride is carried out in the presence of a quaternary ammonium salt and a Lewis acid at 90-100°C. However, quaternary ammonium salts are problematic from an environmental point of view and have the following technical disadvantages: owing to sublimation, parts of the plants may become blocked. Furthermore, the salts are hygroscopic, which may lead to water being introduced and to a higher consumption of chlorinating agent.
Finally, the ammonium salts interfere with the distillative purification of the o-chloromethylbenzoyl chlorides.
Carrying out the reaction using thionyl chloride as chlorinating agent is disadvantageous since sulfur dioxide, which has to be worked-up or neutralized, is formed as coproduct in the synthesis. If the chlorinating agent used is phosgene, carbon dioxide, which does not have to be disposed of, is the only byproduct.
EP-A 583 589 describes a process for preparing o-chloromethylbenzoyl chlorides by phosgenation of benzo-fused lactones in the presence of a catalyst at 170-180°C. In contrast to thionyl chloride, phosgene is thermally stable under these conditions; however, the handling of phosgene and its hold up in the condenser at the high temperatures involved is made more difficult by increased safety precautions. Furthermore, under these conditions, the reaction product is under high thermal stress, which may result in its partial decomposition.
In WO 97/12854, triarylphosphine oxides are used as special catalyst type for the reaction, owing to which the use of hydrogen chloride can be dispensed with;
however, this does not result in an improvement in the required reaction conditions with respect to the objectionably high reaction temperatures and the resulting safety precautions required.
It is an object of the present invention to provide an economical process, capable of being carried out on an industrial scale, for preparing o-chloromethylbenzoyl chlorides which does not have the abovementioned disadvantages and still affords high yields.
We have found that this object is achieved by the process mentioned at the outset, which comprises carrying out the reaction with phosgene, its dimers or trimers in the presence of catalytic amounts of a Lewis acid and catalytic amounts of a phosgenation catalyst.
The starting. materials used are benzo-fused lactones (phthalides) of the formula II, R
R
R"
II
in which R1 to R° can be identical or different and are hydrogen (H), Ci-C~-alkyl, halogen (fluorine, chlorine, bromine or iodine) or trifluoromethyl. Preference is given to using unsubstituted phthalide.
The chlorinating agent used is preferably gaseous or liquid phosgene. Furthermore, it is also possible to use dimers (trichloromethyl chloroformate, "diphosgene") or trimers of phosgene (bistrichloromethyl carbonate, "triphosgene") or mixtures of these chlorinating agents.
Suitable phosgenation catalysts are, in particular, nitrogen compounds and phosphorus compounds. Examples which can be considered are N,N-disubstituted formamides, hexaalkylguanidinium salts, trialkylphosphines or triarylphosphines which may be substituted or unsubstituted in the aryl moiety, trialkylphosphine oxides or triarylphosphine oxides which may be substituted or unsubstituted in the aryl moiety, N-substituted imidazoles and substituted or unsubstitited pyridines. Particular preference is given to the pyridines of the formula IIIa, IIIa i N
where R is hydrogen or methyl, and to phosphine oxides of the formula IIIb, O
~~~b R' P R m r Rr r in which R' to R" ' can be identical or different and are C1-C1o-alkyl or unsubstituted or C1-Cq-alkyl-substituted phenyl and the index n is 0 or 1.
Particular preference is given to 3-methylpyridine picoline) and unsubstituted triphenylphosphine oxide.
The use of liquid trialkylphosphine oxides has, in particular, technical advantages (no need to handle solids, easier discharge of the distillation residue during pu.rification). The tri-C6-C$-alkylphosphine oxides available under the trade name Cyanex~ (for example. Cyanex~ 923 from Cyanamide) are, for example, suitable here. Liquid trialkylphosphine oxides combined with Lewes acids, such as tri(C1-Cq-alkyl) borates and boric acid, have been found to be particularly useful.
The phosgenation catalyst is generally added in amounts of from 0.1 to-20 mol%, based on the amount of benzo-fused lactone used, and is preferably added in amounts of from 1 to 10 molo.
Suitable Lewes acids are, in particular, boron compounds, such as, in particular, BF3, BC13 or complexes thereof with oxygen compounds, sulfur compounds or nitrogen compounds, tri(C1-C9-alkyl) borates and boric acid (H3B03) itself. Furthermore suitable are A1C13, alkylaluminum dichlorides and dialkylaluminum chlorides, and heterogeneous Lewis-acidic alumosilicates of the zeolite type. Particular preference is given to BF3, BC13 and complexes thereof with ether (in particular diethyl ether), water (dehydrate), alcohol (in particular methanol), sulfide (in particular dimethyl sulfide) and amine (in particular ethylamine). Particularly suitable are, for example, BF3 etherate and BF3 dehydrate.
The Lewes acid used is particularly preferably boric acid or tri(C1-C4-alkyl) borate. Such processes give excellent yields and have the advantage that the reaction mixtures are free from fluoride ions. Compared to the analogous reaction where the Lewis acid used is BF3, the entire apparatus can be simplified.
The Lewis acid is added in amounts of from 0.1 to 20 mol%, based on the amount of benza-fused lactone used, preferably in amounts of from 0.5 to 5 mol%.
In a further preferred embodiment of the process, the catalyst used is a complex, formed beforehand, of Lewis acid and the phosgenation catalyst. In general, this complex is employed in a concentration of from 0.1 to mol%, based on the amount of benzo-fused lactone used. The catalyst used is preferably a complex of BF3 and a methyl-substituted pyridine, and particular 15 preference is given to the BF3-(3-picoline complex.
If desired, hydrogen chloride can be introduced in parallel to the introduction of phosgene, to accelerate ring-opening. However, the introduction of hydrogen 20 chloride during. the synthesis is preferably dispensed with.
Furthermore, it may be advantageous to employ heterogeneous Lewis-acidic catalysts, such as, for example, zeolites of the faujasite type in which some or all of the exchangeable cations have been replaced by protons. A heterogeneously catalyzed reaction has the advantage that it can be carried out in a fixed bed. The heterogeneous catalyst is employed in amounts of from 0.01 to loo by weight and preferably in amounts of from 0.1 to 1o by weight, based on the amount of benzo-fused lactone used.
The reaction temperature is generally 110-200°C and preferably 130-160°C.
The process is preferably carried out in the absence of a solvent. However, it is possible to add a solvent -which is inert to phosgene. Inert solvents are, for example, aromatic hydrocarbons, such as toluene, o-, m-or p-xylene or mixtures thereof, chlorinated aromatic hydrocarbons, such as chlorobenzene~ or dichloro-benzenes, or cyclic carbonates, such as ethylene carbonate or propylene carbonate.
The process can be carried out either continuously or batchwise.
The examples below serve to illustrate the process in more detail.
General process description for all examples:
In a phosgenation apparatus consisting of a 1 1 double-jacketed reactor fitted with a battery of high-efficiency condensers, in each case 2 mol (268 g) of phthalide were initially charged and molten together with the catalyst system in question. After heating to 140°C, gaseous phosgene was introduced until no more phosgene was consumed (noticeable by a decrease in the internal temperature). The mixture was then stirred at 140°C for 1 hour, and excess phosgene was then stripped at 100°C using nitrogen. In selected examples, the product was isolated by fractional distillation at 1 mbar and 93-95°C.
Example 1 9. 3 g (0. 1 mol, 5 mol o) of ~3-picoline (3-methyl-pyridine) and 7.9 g (0.04 mol, 2 molo) of BF3-diethyl ether complex ("BF3-etherate") were added as catalyst.
Over. a period of 8 h, a total of 218 g (2.18 mol) of gaseous phosgene were introduced at 140-145°C. After the excess phosgene had been stripped, the reaction discharge (387 g) contained 95 GC area s of o-chloromethylbenzoyl chloride and 2.5 GC area o of unreacted phthalide. Distillation of the crude discharge gave 350 g of o-chloromethylbenzoyl chloride (93% of theory) of a purity of 970.
Example 2 392 g (3 mol) of phthalide together with 14 g (0.15 mol) of ~-picoline and 12 g (0.06 mol) of BF3 etherate were heated to 140°C. At 140-145°C, a total of 342 g (3.42 mol) of gaseous phosgene were introduced.
After an extra reaction time of 1 h, the excess phosgene was stripped using nitrogen. The reaction discharge (572 g) contained 97 GC area % of o-chloromethylbenzoyl chloride and 1 GC area % of phthalide.
Example 3 The catalyst added comprised 20 g of a BF3-~-picoline complex, which had been prepared beforehand. Over a period of 6 h, a total of 230 g (2.3 mol) of gaseous phosgene were introduced. After the excess phosgene had been stripped, the reaction discharge (391 g) contained 97.2 GC area % of o-chloromethylbenzoyl chloride and 0.7 GC area % of phthalide. Distillation of the crude discharge gave 334 g of o-chloromethylbenzoyl chloride (880 of theory) of a purity of 98.80.
Example 4 2 mol of phthalide (268 g) were initially charged with 27.8 g of triphenylphosphine oxide (TPPO) (0.1 mol) and 1 g of HY zeolite GE 1967. At 140-149°C, a total of 231 g of gaseous phosgene (2.31 mol) were introduced over a period of 8 h. After an extra stirring time of 1 h at 140°C, the excess phosgene was stripped using nitrogen. The discharge (403 g) contained 78 GC area o of o-chloromethylbenzoyl chloride and 6.8% of phthalide.
Example 5 2 mol of phthalide (268 g) were initially charged with 27.8 g of TPPO (0.1 mol) and 7.9 g (0.04 mol) of BF3 etherate. At 140-150°C, a total of 233 g of gaseous phosgene (2.33 mol) were introduced over a period of 8 h. After an extra stirring time of 1 h at 140°C, the excess phosgene was stripped using nitrogen. The discharge (415 g) contained 88.4 GC area % of o-chloro-methylbenzoyl chloride and O.lo of phthalide.
Fractional distillation of the crude discharge gave 363 g (960 of theory) of o-chloromethylbenzoyl chloride of a purity of 99.80.
Example 6 268 g (2 mol) of phthalide, 9.3 g (0.1 mol) of (3-picoline and 50 ml of a 0.1 molar solution of BC13 in xylene were initially charged. At 140-150°C, a total of 200 g (2 mol) of gaseous phosgene was introduced over a period of 8 h. The mixture was then stirred at 140°C
for another hour. Excess phosgene was stripped using nitrogen, giving a discharge of 398 g having a content of 77.2 GC area % of o-chloromethylbenzoyl chloride and 10.9% of unreacted phthalide.
Example 7 268 g (2 mol) of phthalide, 9.3 g (0.1 mol) of (i-picoline and 3.1 g (0.05 mol) of crystalline boric acid (Riedel de Haen) were initially charged. At 140-150°C, a total of 245 g (2.45 mol) of gaseous phosgene was introduced over a period of 7 h. The mixture was then stirred at 140°C for another hour. Excess phosgene was stripped using nitrogen, giving a discharge of 380 g having a content of 96 GC area % of o-chloro-methylbenzoyl chloride and 1.40 of unreacted phthalide.
Fractional distillation of the crude discharge gave 340 g of o-chloromethylbenzoyl chloride (90% of theory) of a purity of > 970.
Example 8 268 g (2 mol) of phthalide, 27.8 g (0.1 mol) of TPPO
and 3.1 g (0.05 mol) of crystalline boric acid (Riedel de Haen) were initially charged. At 140-150°G, a total of 247 g (2.47 mol) of gaseous phosgene was introduced over a period of 5 h 45 min. The mixture was then stirred at 140°C for another hour. Excess phosgene was stripped using nitrogen, giving a discharge of 411 g having a content of 88 GC area o of o-chloromethylbenzoyl chloride and 0.7a of unreacted phthalide. Fractional distillation of the crude discharge gave 358 g of o-chloromethylbenzoyl chloride (940 of theory) of a purity of 98.50.
Example 9 268 g (2 mol) of phthalide, 27.8 g (0.1 mol) of TPPO
and 5.2 g (0.05 mol) of trimethyl borate (Aldrich) were initially charged. At 140-150°C, a total of 256 g (2.56 mol) of gaseous phosgene was introduced over a period of 7 h. The mixture was then stirred at 140°C
for another hour. Excess phosgene was stripped using nitrogen, giving a discharge of 410 g having a content of 87.6 GC area ~ of o-chloromethylbenzoyl chloride and 1.1o of unreacted phthalide.
Example 10 2 mol of phthalide, 34.8 g (0.1 mol) of cyanex 923 (Cyanamid) and 3.1 g (0.05 mol) of boric acid were initially charged. At 141 to 150°C, a total 257 g (2.57 mol) of phosgene was introduced over a period of 4 h. The mixture was stirred at 140°C for another hour, and excess phosgene was stripped using nitrogen. The ' CA 02393515 2002-06-05 a crude discharge of 417 g was subjected to fractional distillation. This gave 352 g (93~ of theory) of o-chloromethylbenzoyl chloride of a purity of 98.7%.
Example 11 2 mol of phthalide, 34.8 g (0.1 mol) of Cyanex 923 (Cyanamid) and 5.2 g (0.05 mol) of trimethyl borate were initially charged. At 141 to 150°C, a total of 244 g (2.44 mol) of phosgene was introduced over a period of 6 h. The mixture was stirred at 140°C for another hour, and excess phosgene was stripped using nitrogen. The crude discharge of 411 g was subjected to fractional distillation. This gave 357 g (940 of theory) of o-chloromethylbenzoyl chloride of a purity of 97.70.
Comparative Example I compared to WO-A 99/16743 According to the general experimental procedure, 9.1 g of triethylbenzylammonium chloride (TEBA) (0.04 mol, 2 mol%) and 7.9 g of BF3 etherate (0.09 mol, 2 molo) were used as catalyst mixture. Over a period of 11 h, a total of 45 g (0.45 mol) of gaseous phosgene was introduced at a reaction temperature of initially 95 100 ° C ( 3 h ) and then at 14 0 ° C . After an extra reaction time of 1 h at 140°C and stripping of the phosgene, the crude discharge contained only 7.7 GC area % of o-chloromethylbenzoyl chloride and 910 of unreacted phthalide.
Comparative Example I shows that the phosgenation reaction cannot be carried out under the conditions preferred in WO 99/16743.
r Comparative Example II compared with EP-A 583 589 2 mol of phthalide were initially charged with 18.6 g of (3-picoline (0.2 mol, 10 molo). At 142-152°C 209 g (2.1 mol) of gaseous phosgene and 154 g of gaseous HC1 were introduced in parallel over a period of 10 h.
After an extra stirring time and stripping of excess phosgene, the reaction discharge (380 g) contained 86%
of o-chloromethylbenzoyl chloride and 6~ of unreacted phthalide.
Comparative Example II shows that without the addition of a Lewis acid, the reaction proceeds considerably more slowly and with a poorer yield, and that furthermore more phosgenation catalyst is required.
Claims (10)
1. A process for preparing o-chloromethylbenzoyl chlorides of the formula I, in which R1 to R4 can be identical or different and are hydrogen, C1-C4-alkyl, halogen or trifluoro-methyl, by reacting benzo-fused lactones of the formula II, in which R1 to R4 are as defined above, with gaseous or liquid phosgene, its dimers or trimers, which comprises carrying out the reaction in the presence of catalytic amounts of a Lewis acid and catalytic amounts of a phosgenation catalyst.
2. A process as claimed in claim 1, wherein the Lewis acid used is a boron compound.
3. A process as claimed in claim 2, wherein the Lewis acid used is boron trifluoride or boron trichloride in coordinate form.
4. A process as claimed in claim 2, wherein the Lewis acid used is boric acid or a tri-C1-C4-alkyl borate.
5. A process as claimed in claim 1, wherein the Lewis acid used is an alumosilicate of the zeolite type.
6. A process as claimed in any .of claims 1 to 5, wherein the Lewis acid is employed in a concentration of from 0.1 to 20 mol%, based on the lactone II.
7. A process as claimed in any of claims 1 to 3, wherein the catalyst used is from 0.1 to 20 mole%
of a complex of Lewis acid and phosgenation catalyst.
of a complex of Lewis acid and phosgenation catalyst.
8. A process as claimed in any of claims 1 to 6, wherein the phosgenation catalyst used is a pyridine of the formula IIIa or a phosphine (oxide) of the formula IIIb, where in the formula IIIa, R is hydrogen or methyl, and in the formula IIIb, R' to R''' can be identical or different and are C1-C10-alkyl or unsubstituted or C1-C4-alkyl-substituted phenyl and the index n is 0 or 1.
9. A process as claimed in claim 8, wherein the phosgenation catalyst used is 3-methylpyridine (.beta.-picoline), triphenylphosphine oxide or a liquid trialkylphosphine oxide.
10. A process as claimed in any of claims 1 to 8, wherein from 0.1 to 20 mol% of the phosgenation catalyst, based on the lactone II, are used.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19958757.4 | 1999-12-07 | ||
| DE19958757 | 1999-12-07 | ||
| DE10007694.7 | 2000-02-19 | ||
| DE10007694 | 2000-02-19 | ||
| PCT/EP2000/011817 WO2001042185A2 (en) | 1999-12-07 | 2000-11-27 | Method for producing o-chloromethyl benzoic acid chlorides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2393515A1 true CA2393515A1 (en) | 2001-06-14 |
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ID=26004427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002393515A Abandoned CA2393515A1 (en) | 1999-12-07 | 2000-11-27 | Method for producing o-chloromethyl benzoic acid chlorides |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US7034181B1 (en) |
| EP (1) | EP1265837B1 (en) |
| JP (1) | JP4658432B2 (en) |
| KR (1) | KR100675245B1 (en) |
| CN (1) | CN1176896C (en) |
| AT (1) | ATE268747T1 (en) |
| AU (1) | AU1524201A (en) |
| BR (1) | BR0016244B1 (en) |
| CA (1) | CA2393515A1 (en) |
| CZ (1) | CZ20021978A3 (en) |
| DE (1) | DE50006775D1 (en) |
| DK (1) | DK1265837T3 (en) |
| ES (1) | ES2222929T3 (en) |
| HU (1) | HUP0203591A3 (en) |
| IL (2) | IL149503A0 (en) |
| MX (1) | MXPA02004965A (en) |
| PL (1) | PL357592A1 (en) |
| WO (1) | WO2001042185A2 (en) |
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| KR101430949B1 (en) * | 2005-12-01 | 2014-08-18 | 바스프 에스이 | Method for producing sulfonamides |
| US8575366B2 (en) | 2009-02-05 | 2013-11-05 | Basf Se | Method for producing 2-halogenomethylphenyl acetic acid derivatives |
| CN102796004A (en) * | 2012-08-28 | 2012-11-28 | 山东凯盛新材料股份有限公司 | Synthesis method for paranitrobenzoyl chloride |
| WO2019233321A1 (en) | 2018-06-05 | 2019-12-12 | 沈阳化工大学 | Trifluoroethyl thioether (sulfoxide) substituted benzene compound and use thereof |
| CN114702380B (en) * | 2022-04-07 | 2024-03-19 | 河南特格纳特科技有限公司 | Method for co-producing p-chlorobenzoyl chloride and hexanoyl chloride and acyl chloride product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2655334B1 (en) * | 1989-12-06 | 1992-02-21 | Poudres & Explosifs Ste Nale | PROCESS FOR THE PREPARATION OF CHLORIDES OF CHLORINATED CARBOXYLIC ACIDS. |
| PH11991042549B1 (en) | 1990-06-05 | 2000-12-04 | ||
| DK0669319T3 (en) | 1990-06-27 | 1999-02-08 | Basf Ag | O-benzyloxymeters and plant protection products containing these compounds |
| DE4223382A1 (en) * | 1992-07-16 | 1994-01-20 | Basf Ag | Process for the preparation of aromatic o-chloromethylcarboxylic acid chlorides |
| SK88096A3 (en) | 1994-01-05 | 1996-12-04 | Ciba Geigy Ag | Pesticidal compounds, preparation method thereof and intermediate products at this method and pesticidal agents containing them |
| ATE236119T1 (en) | 1994-02-04 | 2003-04-15 | Basf Ag | PHENYLESACETIC ACID DERIVATIVES, PROCESSES AND INTERMEDIATE PRODUCTS FOR THE PRODUCTION THEREOF AND MATERIALS CONTAINING THEM |
| DE4412316A1 (en) * | 1994-04-11 | 1995-10-12 | Basf Ag | Process for the preparation of o-chloromethylbenzoic acid chlorides |
| TW337519B (en) * | 1995-10-03 | 1998-08-01 | Novartis Ag | Process for the preparation of chloromethyl carbonyl chlorides |
| DE19539324A1 (en) | 1995-10-23 | 1997-04-24 | Basf Ag | Phenylacetic acid derivatives, processes and intermediates for their preparation and compositions containing them |
| JP3433319B2 (en) * | 1997-09-30 | 2003-08-04 | コリア リサーチ インスティテュート オブ ケミカル テクノロジー | Method for producing o- (carboalkoxy) phenylmethanesulfonyl derivative |
| US6734322B1 (en) * | 1999-12-06 | 2004-05-11 | Basf Aktiengesellschaft | Method for producing o-chloromethyl benzenecarbonyl chlorides |
| WO2001042182A2 (en) * | 1999-12-07 | 2001-06-14 | Basf Aktiengesellschaft | Method for producing o-chloromethyl benzoic acid chlorides |
-
2000
- 2000-11-27 EP EP00977582A patent/EP1265837B1/en not_active Expired - Lifetime
- 2000-11-27 HU HU0203591A patent/HUP0203591A3/en unknown
- 2000-11-27 WO PCT/EP2000/011817 patent/WO2001042185A2/en active IP Right Grant
- 2000-11-27 PL PL00357592A patent/PL357592A1/en not_active IP Right Cessation
- 2000-11-27 AT AT00977582T patent/ATE268747T1/en not_active IP Right Cessation
- 2000-11-27 JP JP2001543487A patent/JP4658432B2/en not_active Expired - Fee Related
- 2000-11-27 DE DE50006775T patent/DE50006775D1/en not_active Expired - Lifetime
- 2000-11-27 CA CA002393515A patent/CA2393515A1/en not_active Abandoned
- 2000-11-27 DK DK00977582T patent/DK1265837T3/en active
- 2000-11-27 CZ CZ20021978A patent/CZ20021978A3/en unknown
- 2000-11-27 ES ES00977582T patent/ES2222929T3/en not_active Expired - Lifetime
- 2000-11-27 IL IL14950300A patent/IL149503A0/en active IP Right Grant
- 2000-11-27 KR KR1020027007183A patent/KR100675245B1/en not_active IP Right Cessation
- 2000-11-27 CN CNB008167125A patent/CN1176896C/en not_active Expired - Fee Related
- 2000-11-27 AU AU15242/01A patent/AU1524201A/en not_active Abandoned
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- 2000-11-27 US US10/130,821 patent/US7034181B1/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| ATE268747T1 (en) | 2004-06-15 |
| AU1524201A (en) | 2001-06-18 |
| CN1407963A (en) | 2003-04-02 |
| CN1176896C (en) | 2004-11-24 |
| BR0016244A (en) | 2002-08-27 |
| HUP0203591A3 (en) | 2006-06-28 |
| HUP0203591A2 (en) | 2003-02-28 |
| KR100675245B1 (en) | 2007-01-29 |
| KR20020061631A (en) | 2002-07-24 |
| US7034181B1 (en) | 2006-04-25 |
| ES2222929T3 (en) | 2005-02-16 |
| BR0016244B1 (en) | 2010-08-24 |
| CZ20021978A3 (en) | 2002-09-11 |
| IL149503A0 (en) | 2002-11-10 |
| JP2003516375A (en) | 2003-05-13 |
| DE50006775D1 (en) | 2004-07-15 |
| IL149503A (en) | 2007-02-11 |
| JP4658432B2 (en) | 2011-03-23 |
| EP1265837B1 (en) | 2004-06-09 |
| WO2001042185A3 (en) | 2002-05-02 |
| DK1265837T3 (en) | 2004-10-25 |
| MXPA02004965A (en) | 2002-09-18 |
| EP1265837A2 (en) | 2002-12-18 |
| WO2001042185A2 (en) | 2001-06-14 |
| PL357592A1 (en) | 2004-07-26 |
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